Complex diaryl guanidine metal salt addition compounds and preparation thereof



Patented Oct. 14, 1941 yam COMPLEX martyr. GUANIDINE METAL SALT ADDITIONcoMPonNps AND PREPARA- TION THEREOF Arnold R. Davis, Old Greenwich;Conn, assignor to American Cyanamid Company, New York, N. Y., acorporation ofMaine No Drawing. Application August 3, 1940, Serial No.351,156

6 Claims. (crest-429) This invention relates to complex additionsentially glassy and amorphous or essentially 1.

crystalline.

The salts of the present invention in their powdered form are useful asdelayed action activators for the diaryl guanidine activatableaccelerators, e. benzothiazyl disulfide, in the vulcanization of rubber.In my copending application, Serial No. 223,206, filed August 5, 1938 Ihave claimed the process of vulcanizing rubber with the aid of theamorphous complex addition compounds of a diaryl guanidine and zincchloride.

The following examples will serve to illustrate the invention, to whichhowever it is not to be restricted and in which the parts are by weight.

Example 1 28.76 parts (1 mole) of zinc sulfate as ZIISO4.7H2O and 47.83parts (2 moles) of di-otolyl guanidine were ground and then heated to175 C. over a period of 60 minutes, water being given off from themixture. A glassy product was obtained.

Example 2 26.66 parts (1 mol) of aluminum sulfate as A12(SO4)3.18H2O and50.71 parts (3 mols) of diphenyl guanidine were ground together and thenheated to a maximum temperature of 150 C. during a total heating periodof 55 minutes, the mixture being held between 140 and 150 C. forminutes. Water was given ofi during the fusion and a somewhat cloudy andglassy greycolored product was formed which had a softening point of 110C.

Example 3 24.14 parts (1 mol) of aluminum chloride, AlC13.6H2O and 71.75parts (3 mols) of di-o-tolyl guanidine were ground together and thenheated to a maximum of 180 C. during a total heating period of 1 hourand minutes. The mixture g. mercaptobenzothiazol and 1 was held betweenand 160 C. for 20 minutes, then heated to 180 C. for 10 minutes andcooled to C. in 23 minutes and poured onto tin foil to cool.

Water was given off during the heating and the product was apinkish-colored and somewhat glassy material with a softening point ofl49-154 C. The product on standing became essentially crystalline. 1

' Example4 I 22.84 parts (1 mol) of cadmium chloride as CdC12.2.5I-I2O*and 47.83 parts (2 mols) of di-otolyl guanidine' were ground togetherand then heated to a maximum temperature of C. during a total heatingperiod of 2 hours and 40 minutes. The mixture was held between 150-160C. for 15 minutes, then put in the oven at 100 C. for 25 minutes andfurther heated at about 150 C. for 1 hour.

Water was given off during the early part of the heating and theproduct, which was a clear reddish-colored glassy material, had asoftening point of 75'77 C.

Example 5 22.56 parts .(1 mol) of stannous chloride, SnClaZHzO and 47.83parts (2 mole) of di-otolyl guanidine were ground together and thenheated to a maximum of about 160 C. during a total heating time of 1hour and 10 minutes. The mixture was held for 10 minutes at 150-160 C.and the product was a brown, glass-like material which appeared somewhatsoluble in water and had a softening point of -175 C. No water appearedto be given off during the heating. The product on standing becameessentially crystalline.

Example 6 17.53 parts (1 mol) of stannic chloride as SnCl4.5I-IzO and47.83 parts (4 mols) of di-otolyl guanidine were ground and then heatedto a maximum temperature of 160 C. during a total heating period of 1hour. The mixture was held for 35 minutes at 150-160 C. The product wasa light-colored glassy resin which appeared to be somewhat soluble inwater and had a softening point of 156 C. The product on standing becameessentially crystalline.

Example 7 27.2 parts of zinc chloride were powdered with 23.9 parts ofdi-o-tolyl guanidine to get the zinc chloride as fine as possible andthe balance of the cli-o-tolyl guanidine, 71.7 parts, were mixed withthe powdered material. This mixture was then heated by means of an oilbath, the starting temperature of the oil bath being 110 C. After 45minutes the mass was liquid with a temperature of 118 C. The temperatureof the mass was allowed to drop to about 80 C. in 30 minutes and thenthemass was heated to 100 C. in 1 hour and 10 minutes and held at 110 C.for 2 hours. This gave a glassy amorphous product.

Any diaryl guanidine may be fused with any of themetal salts recitedinthe examples and also with cadmium sulfate, stannous sulfate and stannicsulfate in the manner described in the examples to obtainnon-hygroscopic complex addition compounds, reacting equivalents of thediaryl guanidine and the metal salts being em: ployed.

It is to be noted that the heating times given to contain some of theunreacted crystalline metal chloride or sulfate, the heating may becontinued to insure the complete reaction and removal of the crystallinemetal salt or in the case of an already cooled product this may bereheated to fusion for an additional time sufllcient to react and thuseliminate the crystalline metal salt.

Suitable changes may be made in carrying out my invention withoutdeparting from the spirit and scope thereof.

What I claim is:

1. The complex addition compounds of a diaryl guanidine and a salt ofthe group consisting of the chlorides and sulfates of zinc, aluminum,cadmium and tin.

2. The complex addition compounds of a diaryl guanidine and zincchloride.

.3. The amorphous addition compound, di-otolyl guanidine and zincchloride.

4. A process of preparing complex addition compounds of a diarylguanidine and an acidic metal salt which comprises heating to fusion atdiarylguanidine and a salt of the group consisting of the chlorides andsulfates of zinc, aluminum, cadmium and tin.

5. A process of preparing amorphous complex addition compounds of adiaryl 'guanidine and zinc chloride which comprises heating to fusion adiaryl guan'idine and zinc chloride.

6. A process of preparing the amorphous complex addition compound ofdi-o-tolyl .guanidine and zinc chloride which comprises heating thesematerials to fusion.

ARNOLD R. DAVIS.

CERTIFICATE OF CORRECTION. Patent No. 2,259,065. October 1b., 19L .l.

ARNOLD R. DAVIS.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: age 2,sec- 0nd column, line 15, claim 5, for "guanidine and zinc chloride."read that the said Letters Patent should be that the same may conform tothe record -'guanidine.zinc chloride.-; and read with this correctiontherein of the case in the Patent Office.

Signed and sealed this 25th day of November, A. D. l9LLl Henry VanArsdale,

(Seal) Y Acting Commissioner of Patents.

